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United States Patent |
5,648,453
|
Saida
,   et al.
|
July 15, 1997
|
Electroconductive polymer and process for producing the polymer
Abstract
Electroconductive polymers having a chemical structure represented by, for
example, the formula (I)
##STR1##
wherein R.sup.1 and R.sup.2 independently represent H, a C.sub.1 to
C.sub.20 alkyl or alkoxy group, an amino group, a trihalomethyl group or a
phenyl group, X represents S, O, Se, Te or NR.sub.3 R.sub.3 represents H,
a C.sub.1 to C.sub.6 alkyl group or an aryl group, M represents a cation
such as M.sup.+, an alkali metal ion or a quaternary ammonium ion, and m
is 0.2 to 2 and a process for producing the polymer.
Inventors:
|
Saida; Yoshihiro (Chiba, JP);
Ikenoue; Yoshiaki (Chiba, JP);
Ichikawa; Reiko (Osaka, JP)
|
Assignee:
|
Showa Denko K.K. (Tokyo, JP)
|
Appl. No.:
|
476977 |
Filed:
|
June 7, 1995 |
Foreign Application Priority Data
| Dec 04, 1991[JP] | 3-348295 |
| Nov 24, 1992[JP] | 4-336672 |
| May 31, 1993[JP] | 5-129798 |
Current U.S. Class: |
528/380; 525/410; 525/417; 525/535; 525/540; 528/388; 528/417; 528/423; 528/424 |
Intern'l Class: |
C08G 075/00; C08G 063/91 |
Field of Search: |
525/410,417,535,540
528/380,388,417,423,424
|
References Cited
U.S. Patent Documents
4833231 | May., 1989 | Yoshida et al.
| |
4880508 | Nov., 1989 | Aldissi.
| |
4954594 | Sep., 1990 | Yoshida et al.
| |
5115057 | May., 1992 | Ono et al.
| |
5256454 | Oct., 1993 | Murai et al.
| |
Foreign Patent Documents |
0164974 | Dec., 1985 | EP.
| |
0273643 | Jul., 1988 | EP.
| |
0399463 | Nov., 1990 | EP.
| |
63-307604 | Dec., 1988 | JP.
| |
2-242816 | Sep., 1990 | JP.
| |
2-252727 | Oct., 1990 | JP.
| |
2258833 | Oct., 1990 | JP.
| |
2258832 | Oct., 1990 | JP.
| |
8705914 | Oct., 1987 | WO.
| |
Other References
Journal or American Chemical Society, vol. 109, p. 1858, 1987.
Polymer Bulletin, vol. 18, p. 277, 1987.
Journal of Chemical Society, Chemical Communication, p. 621, 1987.
Journal of Chemical Society, Chemical Communication, p. 180, 1990.
Synthetic Metals, vol. 31, p. 369, 1989.
Journal of Americain Chemical Society, vol. 112, p. 2800, 1990.
Journal of Organic Chemistry, vol. 49, p. 33882, 1984.
Journal of Chemical Physics, vol. 85, p. 4673, 1986.
Journal of American Chemical Society, vol. 110, p. 2983.
Journal of American Chemical Society, vol. 113, p. 7411, 1991.
Journal of Electrochemical Society, vol. 137, p. 900, 1990.
Polymer Communications, vol. 32, p. 412, 1991.
New Journal of Chemistry, vol. 15, p. 233, 1991.
Polymer Bulletin, vol. 18, 1987, Heidelberg, DE pp. 277-281, E.E. Havinga
et al., "Self-doped water-soluble conducting polymers."
|
Primary Examiner: Lee; Helen
Attorney, Agent or Firm: Sughrue, Mion, Zinn, Macpeak & Seas
Parent Case Text
CROSS-REFERENCE TO RELATED APPLICATION
This application is a continuation-in-part of application Ser. No.
08/251,297, filed May 31, 1994, and of application Ser. No. 07/985,339,
filed Dec. 4, 1992, both are now abandoned.
Claims
We claim:
1. A process for producing a polymer having a chemical structure
represented by the formula (I):
##STR17##
wherein R.sup.1 and R.sup.2 independently represent a hydrogen atom, a
linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms, a
primary, secondary or tertiary amino group, a trihalomethyl group, a
phenyl group or a substituted phenyl group wherein said substituted phenyl
group is an alkyl-substituted phenyl group, X represents S, O, Se, Te, or
NR.sup.3, R.sup.3 represents a hydrogen atom, a linear or branched alkyl
group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl
group wherein said substituted aryl group is an alkyl-substituted aryl
group, providing that the chain in the alkyl group of R.sup.1, R.sup.2 or
R.sup.3 or in the alkoxy group of R.sup.1 or R.sup.2 optionally contains
another carbonyl, ether or amide moiety, M represents H.sup.+, an alkali
metal ion or a cation and m represents a numerical value in the range
between 0.2 to 2;
which process comprises reacting a sulfonating agent with a compound having
the formula (IV):
##STR18##
wherein R.sup.1 and R.sup.2 independently represent a hydrogen atom, a
linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms, a
primary, secondary or tertiary amino group, a trihalomethyl group, a
phenyl group or a substituted phenyl group wherein said substituted phenyl
group is an alkyl-substituted phenyl group, Y represents S, O, Se, Te,
S.dbd.O, Te.dbd.O or NR.sup.3, R.sup.3 represents a hydrogen atom, a
linear or branched alkyl group having 1 to 6 carbon atoms or a substituted
or unsubstituted aryl group wherein said substituted aryl group is an
alkyl-substituted aryl group, providing that the chain in the alkyl group
of R.sup.1, R.sup.2 or R.sup.3 or in the alkoxy group of R.sup.1 or
R.sup.2 optionally contains a carbonyl, ether or amide moiety.
2. A process for producing a polymer according to claim 1 having a chemical
structure represented by the formula (I), which process comprises reacting
a sulfonating agent with a compound having the formula (V):
##STR19##
wherein R.sup.1 and R.sup.2 independently represent a hydrogen atom, a
linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms, a
primary, a secondary or tertiary amino group, a trihalomethyl group, a
phenyl group or a substituted phenyl group, wherein said substituted
phenyl group is an alkyl-substituted phenyl group, X represents S, O, Se,
Te or NR.sup.3, and R.sup.3 represents a hydrogen atom, a linear or
branched alkyl group having 1 to 6 carbon atoms or a substituted or
unsubstituted aryl group wherein said substituted aryl group is an
alkyl-substituted aryl group, providing that the chain in the alkyl group
of R.sup.1, R.sup.2 or R.sup.3 or in the alkoxy group of R.sup.1 or
R.sup.2 optionally contains a carbonyl, ether or amide moiety.
3. A process for producing an electroconductive polymer comprising at least
one structural unit represented by formula (VII) as a repeating unit,
##STR20##
wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 each independently
represents a monovalent member selected from the group consisting of a
hydrogen atom, a linear or branched, saturated or unsaturated alkyl,
alkoxy or alkyl ester group each having from 1 to 20 carbon atoms,
SO.sub.3 --M.sup.1, a halogen atom, a nitro group, a cyano group, a
primary, secondary or tertiary amino group, a trihalomethyl group, and a
substituted or unsubstituted phenyl group wherein said substituted phenyl
group is an alkyl-substituted phenyl group, with the proviso that two or
more of R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are not SO.sub.3
--M.sup.1 simultaneously, wherein two of R.sup.4, R.sup.5, R.sup.6,
R.sup.7 and R.sup.8 may combine with each other at any optional position
to form at least one divalent chain which forms, together with two carbon
atoms of the ring substituted with R.sup.4 -R.sup.8, at least one 3- to
7-membered saturated or unsaturated hydrocarbon ring structure, and the
alkyl group, the alkoxy group, or the alkyl ester group represented by
R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 may optionally include a
carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl or imino
moiety; M.sup.1 represents H.sup.+, an aklali metal ion, or a cation of a
Vb Group element unsubstituted or substituted with an alkyl group having
from 1 to 30 carbon atoms, or with an aryl group having from 6 to 30
carbon atoms; and r represents an integer of from 0 to 3, and indicates
the number of condensed rings enclosed by the thiophene ring and the
benzene ring having substituents of R.sup.4, R.sup.5, R.sup.6, wherein the
condensed ring in the formula may optionally contain a nitrogen atom or an
N-oxide group, by polymerizing a compound represented by formula (VI):
##STR21##
wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8, M.sup.1 and r each
has the same meaning as defined above; and X.sup.1, X.sup.2, X.sup.3 and
X.sup.4 each independently represents a hydrogen atom or a halogen atom.
4. A process for producing an electroconductive polymer comprising at least
one structural unit represented by the formula (VIII) as a repeating unit:
##STR22##
wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 each independently
represents a monovalent member selected from the group consisting of a
hydrogen atom, a linear or branched, saturated or unsaturated alkyl,
alkoxy or alkyl ester group each having from 1 to 20 carbon atoms,
SO.sub.3 --M.sup.1, a halogen atom, a nitro group, a cyano group, a
primary, secondary or tertiary amino group, a trihalomethyl group, and a
substituted or unsubstituted phenyl group wherein said substituted phenyl
group is an alkyl-substituted phenyl group, with the proviso that two or
more of R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 are not SO.sub.3
--M.sup.1 simultaneously, wherein two of R.sup.4, R.sup.5, R.sup.6,
R.sup.7 and R.sup.8 may combine with each other at any optional position
to form at least one divalent chain which forms, together with two carbon
atoms of the ring substituted with R.sup.4 -R.sup.8, at least one 3- to
7-membered saturated or unsaturated hydrocarbon ring structure, and the
alkyl group, the alkoxy group, or the alkyl ester group represented by
R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 may optionally include a
carbonyl, ether, ester, amide, sulfide, sulfinyl, sulfonyl or imino
moiety; M.sup.1 represents H.sup.+, an alkali metal ion, or a cation of a
Vb Group element unsubstituted or substituted with an alkyl group having
from 1 to 30 carbon atoms, or with an aryl group having from 6 to 30
carbon atoms; r represents an integer of from 0 to 3, and indicates the
number of condensed rings enclosed by the thiophene ring and the benzene
ring having substituents of R.sup.4, R.sup.5 and R.sup.6, wherein the
condensed ring in the formula may optionally contain a nitrogen atom or an
N-oxide group; Ar represents a repeating unit of a .pi.-electron
conjugated system having no sulfonic acid group; and p and q represent
molar fractions of the respective repeating units in the copolymer, and
thus do not denote a block copolymer,
by polymerizing a compound represented by formula (VI):
##STR23##
wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, M.sup.1 and r each
has the same meaning as defined above, and X.sup.1, X.sup.2, X.sup.3 and
X.sup.4 each independently represents a hydrogen atom or a halogen atom,
alone or together with another aromatic compound and/or heterocyclic
compound and/or compound capable of forming a .pi.-electron conjugated
structure.
5. The process for producing an electroconductive polymer as claimed in
claim 3, wherein the electroconductive polymer comprises at least one
structural unit represented by formula (VII), wherein r is 0, as a
repeating unit.
6. A process for producing an electroconductive polymer comprising at least
one structural unit represented by formula (IX):
##STR24##
wherein R.sup.4, R.sup.5, and R.sup.6 each independently represents a
monovalent member selected from the group consisting of a hydrogen atom, a
linear or branched, saturated or unsaturated alkyl, alkoxy or alkyl ester
group each having from 1 to 20 carbon atoms, SO.sub.3 --M.sup.1, a halogen
atom, a nitro group, a cyano group, a primary, secondary or tertiary amino
group, a trihalomethyl group, and a substituted or unsubstituted phenyl
group wherein the substituted phenyl group is an alkyl-substituted phenyl
group, with the proviso that two or more of R.sup.4, R.sup.5 and R.sup.6
are not SO.sub.3 --M.sup.1 simultaneously, wherein two of R.sup.4, R.sup.5
or R.sup.6 may combine with each other at any optional position to form at
least one divalent chain which forms, together with two carbon atoms of
the ring substituted with R.sup.4 -R.sup.8, at least one 3- to 7-membered
saturated or unsaturated hydrocarbon ring structure, and the alkyl group,
the alkoxy group, or the alkyl ester group represented by R.sup.4, R.sup.5
and R.sup.6 may optionally include a carbonyl, ether, ester, amide,
sulfide, sulfinyl, sulfonyl or imino moiety; M.sup.1 represents H.sup.+,
an alkali metal ion, or a cation of a Vb Group element unsubstituted or
substituted with an alkyl group having from 1 to 30 carbon atoms, or with
an aryl group having from 6 to 30 carbon atoms; Ar represents a repeating
unit of a .pi.-electron conjugated system having no sulfonic acid group;
and m and n represent molar fractions of the respective repeating units in
the copolymer, and thus do not denote a block copolymer,
by polymerizing a compound represented by formula (VI):
##STR25##
wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8 and M.sup.1 each has
the same meaning as defined above; and X.sup.1, X.sup.2, X.sup.3 and
X.sup.4 each independently represents a hydrogen atom or a halogen atom,
and r is 0, alone or together with another aromatic compound and/or
heterocyclic compound and/or compound capable of forming a .pi.-electron
conjugated structure.
7. The process for producing an electroconductive polymer as claimed in
claim 3, wherein the electroconductive polymer comprises at least one
structural unit represented by formula (VII), wherein r is 1, as a
repeating unit.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention in one embodiment relates to an electroconductive
polymer having a high stability and exhibiting high solubility in water
and also relates to a process for producing the polymer. More
specifically, the present invention in this embodiment relates to a
water-soluble electroconductive polymer particularly suitable for use as
electrodes, sensors, electronic display elements, nonlinear optical
elements, photoelectric conversion elements, antistatic agents, conducting
materials, and optical materials which require high workability in the
field of electric and electronic industry and a process for producing the
polymer.
The present invention in another embodiment relates to an extremely stable
electroconductive polymer having high solvent solubility and to a process
for producing the polymer. More specifically, the present invention
relates to the polymer and to a process for producing an electroconductive
polymer particularly suitable as an electrode, a sensor, an electronics
display element, a non-linear optical element, a photoelectric conversion
element, or an antistatic agent, which encounters severe processability
requirements in the field of electric and electronic industries, as well
as being suitable for various electroconductive or optical materials.
2. Description of the Related Art
Polymers of an advanced .pi. electron conjugate system have attracted
attention in industries concerned due to their characteristics such as not
only conductivity but also behavior manifested in the change of state
during the metal/semiconductor transition. Thus, studies have been made
with a view to developing these polymers suitable for varying
applications. Among other polymers of this class, water-soluble
self-doping conjugate type polymers which are obtained by having a
Bronsted acid group joined to the main chain of polymer by covalent bond
either directly or indirectly with the aid of a spacer have arrested a
particular interest in respect that they possess stable
electroconductivity over a long period without needing contribution of any
external dopant.
Specific examples thereof include a polythiophene derivative having an
alkanesulfonic acid group (F. Wudl et al., Journal of American Chemical
Society, vol. 109, p. 1858, 1987; and E. E. Havinga et al., Polymer
Bulletin, vol. 18, p. 277, 1987), a polythiophene derivative or a
polypyrrole derivative (Aldissi, U.S. Pat. No. 4,880,508), a polymer
having an alkanesulfonic acid group or an alkylcarboxyl acid group as a
substituent in an aromatic ring of polyaniline (WO 87/05914;
JP-A-63-39916), a polymer having a propanesulfonic acid group substituted
at the N-position of pyrrole (J. Chem. Soc., Chemical Communication, p.
621, 1987), a polyaniline derivative having a propanesulfonic acid group
substituted at the N-position (J. Chem. Soc., Chemical Communication, p.
180, 1990 and Synthetic Metals, vol. 31, p. 369, 1989), a polyaniline
derivative having a sulfonic acid group substituted directly on the
aromatic ring (J. Am. Chem. Soc., vol. 112, p. 2800, 1990), and a
polycarbazole derivative having an alkanesulfonic acid group substituted
at the N-position (U.S. Pat. No. 5,130,412). In addition, their production
processes are also disclosed in these publications.
Furthermore, an oxidative chemical polymerization of a thiophene derivative
monomer having an alkanesulfonic acid group is disclosed in JP-A-2-189333.
Further, among condensed heteropolycyclic compounds, isothianaphthene,
benzo[c]furan, and naphtho[2,3-c]thiophene, each having a .pi.-conjugated
quinoid structure, are known to have a very high reactivity, and require
specific procedures for their isolation (see, J. Org. Chem., vol. 36, p.
3932, 1971, and Recl. Trav. Chim. Pays-Bas, vol. 87, p. 1006, 1968).
As a specified example of bicyclic conducting polymers,
polyisothianaphthene is disclosed in conjunction with a method for the
production thereof in J. Org. Chem., 49, 3382 (1984), in which it is
described to possess a stable conductivity as evidenced by an extremely
small energy gap of 1.1 eV. However, polyisothianaphthene is neither
soluble nor fusible and is extremely deficient in moldability. A method
for rendering this particular polymer soluble in an organic solvent by
introducing an alkyl group or alkoxy group into the polymer is disclosed
in JP-A-2-242816. The term "JP-A" as used herein means an "unexamined
published Japanese patent application".
The thought that the conductivity of such isothianaphthene polymers is
further influenced by introducing an electron attracting or donating group
into the isothianaphthene backbone has been reported in conjunction with
results of calculation by Bredas et al. in J. Chem. Phys., 85(8)., 4673
(1986). As examples of the polymers relating to such isothianaphthene
polymers, polymers having a halogen atom as a substituent as disclosed in
JP-A-63-307604 and polymeric compounds possessing an isothianaphthene
backbone having an electron attracting group as a substituent as described
in JP-A-02-252727 may be cited. A process for producing a polymer having a
naphtho[2,3-c]thiophene structure, which is a heterotricyclic
electroconductive polymer that is neither soluble nor fusible, has been
reported in Synthetic Metals, vol. 35, p. 263, 1990. The oxidative
chemical polymerization of 1,3-dihydroisothianaphthene without a sulfonic
acid group is disclosed, for example, in JP-A-63-118323 and U.S. Pat. No.
4,789,748. Bicyclic water-soluble conducting polymers, having an
isothianaphthenylene structure, an isobenzofurylene structure, an
isoindolylene structure, an isobenzoselenylene structure, or an
isobenzotellurylene structure as a repeating unit thereof, have never been
disclosed to the art to date. Neither of these patent publications has any
specific disclosure of the polymer having a sulfonic acid group on
repeating unit of the present invention nor of a method for the production
of such a polymer.
SUMMARY OF THE INVENTION
Accordingly, a first object of the present invention is to eliminate the
above-mentioned disadvantages of the prior art and to provide a practical
and novel bicyclic water-soluble electroconductive polymer derived from a
known compound, a process for producing the polymer and an article
processed therefrom.
A further object of the present invention is to provide an
electroconductive polymer and a process for producing an electroconductive
polymer comprising a condensed heteropolycyclic monomer unit having a
sulfonic acid group by polymerizing a sulfonic acid group-containing
condensed heteropolycyclic compound as a starting material.
Another object of the present invention is to provide a process for
producing an electroconductive polymer comprising a condensed
heteropolycyclic monomer unit having a sulfonic acid group by polymerizing
a sulfonic acid group-containing condensed heteropolycyclic compound as a
starting material alone or together with another aromatic compound and/or
heterocyclic compound and/or compound capable of forming a .pi.-electron
conjugated structure.
Other objects and advantages of the present invention will be apparent from
the following description.
In accordance with a first embodiment of the present invention, there is
provided a water-soluble electroconductive polymer having a chemical
structure represented by the formula (I):
##STR2##
wherein R.sup.1 and R.sup.2 independently represent a hydrogen atom, a
linear or branched alkyl or alkoxy group having 1 to 20 carbon atoms, a
primary, secondary or tertiary amino group, a trihalomethyl group, a
phenyl group or a substituted phenyl group, X represents S, O, Se, Te or
NR.sup.3, R.sup.3 represents a hydrogen atom, a linear or branched alkyl
group having 1 to 6 carbon atoms or a substituted or unsubstituted aryl
group, providing that the chain in the alkyl group of R.sup.1, R.sup.2 or
R.sup.3 or in the alkoxy group of R.sup.1 or R.sup.2 optionally contains a
carbonyl, ether or amide bond, M represents H.sup.+, an alkali metal ion
such as Na.sup.+, Li.sup.+ or K.sup.+ or a cation such as a quaternary
ammonium ion, and m represents a numerical value in the range between 0.2
and 2.
In accordance with a second embodiment of the present invention, there is
also provided a water-soluble electroconductive polymer having a chemical
structure represented by the formula (II):
##STR3##
wherein R.sup.1, R.sup.2, X, R.sup.3, M, and m have the same meanings as
defined above with respect to the formula (I) and k is a numerical value
smaller than that of m, and/or the formula (III):
##STR4##
wherein R.sup.1, R.sup.2, X, R.sup.3, M, and m have the same meanings as
defined above with respect to the formula (I), .delta. is a numerical
value not more than 0.7, Z represents an anion, and j represents a
numerical value 1 or 2 indicating the valency of the anion Z, as obtained
by electrochemically and/or chemically doping the above-mentioned polymer
having a chemical structure represented by the formula (I).
In accordance with a third embodiment of the present invention, there is
provided a process for producing the water-soluble electroconductive
polymer mentioned above, which process comprises reacting a sulfonating
agent with a compound having the formula (IV):
##STR5##
wherein R.sup.1, R.sup.2, and R.sup.3 have the same meanings as defined
above with respect to the formula (I) and Y represents S, O, Se, Te,
S.dbd.O, Se.dbd.O, Te.dbd.O or NR.sup.3 and the general formula (V):
##STR6##
wherein R.sup.1, R.sup.2, X and R.sup.3 have the same meanings as defined
above with respect to the formula (I) or on at least one compound selected
from the compounds mentioned above.
The present invention in a fourth embodiment provides an electroconductive
polymer comprising at least one structural unit represented by formula
(VII) as a repeating unit and a process for producing such, which
comprises polymerizing a compound represented by formula (VI):
##STR7##
wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8 each independently
represents a monovalent group selected from the group consisting of a
hydrogen atom, a linear or branched, saturated or unsaturated alkyl,
alkoxy, or alkyl ester group each having from 1 to 20 carbon atoms,
preferably from 1 to 12 carbon atoms, SO.sub.3 --M.sup.1, a halogen atom,
a nitro group, a cyano group, a primary, secondary or tertiary amino
group, a trihalomethyl group, and a substituted or unsubstituted phenyl
group, with the proviso that two or more of R.sup.4, R.sup.5, R.sup.6,
R.sup.7 and R.sup.8 are not SO.sub.3 --M.sup.1 simultaneously, wherein the
hydrocarbon chain represented by R.sup.4, R.sup.5, R.sup.6, R.sup.7 or
R.sup.8 may combine with each other at any optional position to form at
least one divalent chain which forms, together with two carbon atoms of
the substituted ring, at least one 3- to 7-membered saturated or
unsaturated hydrocarbon ring structure, and the alkyl group, the alkoxy
group, or the alkyl ester group represented by R.sup.4, R.sup.5, R.sup.6,
R.sup.7 and R.sup.8, or the cyclic hydrocarbon chain formed therefrom may
optionally have a bond giving rise to a carbonyl, ether, ester, amide,
sulfide, sulfinyl, sulfonyl or imino moiety; wherein X.sup.1, X.sup.2,
X.sup.3 and X.sup.4 each independently represents a hydrogen atom or a
halogen atom; wherein M.sup.1 represents H.sup.+, an alkali metal ion,
such as Na.sup.+, Li.sup.+ and K.sup.+, or a cation of a Vb Group element
unsubstituted or substituted with an alkyl group having from 1 to 30
carbon atoms, preferably from 1 to 20 carbon atoms, and more preferably
from 1 to 12 carbon atoms, or with an aryl group having from 6 to 30
carbon atoms, preferably from 6 to 20 carbon atoms, more preferably from 6
to 16 carbon atoms, such as NH.sub.4.sup.+, NH(CH.sub.3).sub.3.sup.+,
N(CH.sub.3).sub.4.sup.+, NH(C.sub.2 H.sub.5).sub.3.sup.+, N(C.sub.6
H.sub.5).sub.4.sup.+, PH.sub.4.sup.+, P(CH.sub.3).sub.4.sup.+, P(C.sub.6
H.sub.5).sub.4.sup.+, AsH.sub.4.sup.+, As(CH.sub.3).sub.4.sup.+ and
As(C.sub.6 H.sub.5).sub.4.sup.+ ; and wherein r represents an integer of
from 0 to 3, and indicates the number of condensed rings enclosed by the
dihydrothiophene ring and the benzene ring having substituents R.sup.4,
R.sup.5 and R.sup.6, wherein the condensed ring in the formula may
optionally contain nitrogen or an N-oxide:
##STR8##
wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, M.sup.1 and r each
has the same meaning as defined above.
The present invention in a fifth embodiment also provides a process for
producing an electroconductive polymer comprising a chemical structure
represented by formula (VIII):
##STR9##
wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, M.sup.1 and r each
has the same meaning as described above, Ar represents a repeating unit of
a .pi.-electron conjugated system having no sulfonic acid group, p and q
represent molar fractions of the respective repeating units in the
copolymer, and thus do not denote a block copolymer and a process for
producing such by polymerizing a compound represented by formula (VI),
wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, X.sup.1, X.sup.2,
X.sup.3, X.sup.4, M.sup.1 and r each has the same meaning as described
above, alone or together with another aromatic compound and/or
heterocyclic compound and/or compound capable of forming a .pi.-electron
conjugated structure.
The present invention further provides in a sixth embodiment an
electroconductive polymer comprising a chemical structure represented by
formula (IX):
##STR10##
wherein R.sup.4, R.sup.5, R.sup.6, M.sup.1, Ar, p and q each has the same
meaning as described above, by polymerizing a compound represented by
formula (VI), wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8,
X.sup.1, X.sup.2, X.sup.3, X.sup.4 and M.sup.1 each has the same meaning
as described above and r is 0, alone or together with another aromatic
compound and/or heterocyclic compound and/or compound capable of forming a
.pi.-electron conjugated structure.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be better understood from the description set
forth below with reference to the accompanying drawings, wherein:
FIG. 1 is a UV spectrum of the polymer obtained in Example 1;
FIG. 2 is a gel permeation chromatograph of the polymer obtained in Example
1;
FIG. 3 is an infrared absorption spectrum of the polymer obtained in
Example 1;
FIG. 4 shows a cyclic voltammogram performed on the film of the polymer
obtained in Example 1;
FIG. 5 is a UV spectrum of the polymer obtained in Example 2;
FIG. 6 is the visible near infrared absorption spectrum of the polymer
obtained in Example 21;
FIG. 7 is the visible near infrared absorption spectrum of the polymer
obtained in Example 22; and
FIG. 8 is the visible near infrared absorption spectrum of the polymer
obtained in Example 24.
DETAILED DESCRIPTION OF THE INVENTION
The substituents R.sup.1 and R.sup.2 of the polymer having a chemical
structure represented by the formula (I) according to the present
invention are only required to be those inhibiting neither the reaction of
sulfonation nor the polymerization reaction of monomers. For example, they
are independently selected from those among a hydrogen atom, linear or
branched alkyl or alkoxy groups having 1 to 20 carbon atoms, aliphatic or
aromatic primary, secondary or tertiary amino groups, trihalomethyl groups
such as trichloromethyl, phenyl group, and substituted phenyl groups.
Optionally, the above-mentioned alkyl or alkoxy groups may contain a
carbonyl, ether, or amide bond in their chains having 1 to 20 carbon
atoms.
Specific examples of R.sup.1 and R.sup.2 are hydrogen, alkyl groups and
alkoxy groups. More specific examples of such alkyl groups include methyl,
ethyl, propyl, isopropyl, butyl, pentyl, hexyl, octyl, dodecyl,
methoxyethyl, ethoxyethyl, acetonyl, phenacryl and the like, and those of
such alkoxy groups include methoxy, ethoxy, propoxy, isopropoxy, octyloxy,
dodecyloxy and the like.
Other specific examples of R.sup.1 and R.sup.2 include amino groups such as
methylamino, ethylamino, diphenylamino, anilino, and the like,
trifluoromethyl group, phenyl group, tolyl group, xylyl group, acylamido
groups such as acetoamido and the like.
The symbol m which means the ratio of substitution of "sulfo"-containing
group at the benzene ring of the polymer represents a numerical value in
the range between 0.2 and 2, and the range between 0.4 and 1.3 is
preferably represented.
The symbol X in the formula (I) represents S, O, Se, Te or NR.sup.3 and
thus the chemical structure represented by formula (I) is a
isothianaphthenylene, isobenzofurylene, isobenzoselenylene,
isobenzotellurylene, or isoindolylene structure. The substituent R.sup.3
mentioned above represents a linear or branched alkyl group having 1 to 6
carbon atoms or substituted or unsubstituted aryl group. The alkyl groups
in the substituents R.sup.3 may optionally contain a carbonyl, ether, or
amide bond in its chain having 1 to 6 carbon atoms.
Specific examples of R.sup.3 are hydrogen, methyl, ethyl, propyl,
isopropyl, butyl, hexyl, phenyl, tolyl, methoxyethyl, ethyoxyethyl,
acetonyl, acetyl and the like.
The symbol M represents H.sup.+, an alkali metal ion such as Na.sup.+,
Li.sup.+ or K.sup.30 , or a cation such as ammonium or an
alkyl-substituted or aryl-substituted cation of Vb group element such as
N(CH.sub.3).sub.4.sup.+ or N(C.sub.6 H.sub.5).sub.4.sup.+. The conversion
to the specific cation is easily effected by means of an ordinary
ion-exchange resin.
The condensed heteropolycyclic compound represented by formula (VI) is a
compound wherein r of formula (VI), which indicates the number of the
condensed rings enclosed by the dihydrothiophene ring and the benzene ring
having substituents R.sup.4, R.sup.5 and R.sup.6, is an integer of from 0
to 3, and the condensed rings of formula (VI) may optionally contain
nitrogen or an N-oxide. Suitable examples include thieno[3,4-b]quinoxaline
and thieno[3,4-b]quinoxaline-4,9-dioxide. The hydrocarbon chain
represented by R.sup.4, R.sup.5, R.sup.6, R.sup.7 or R.sup.8 may combine
with each other at any optional position to form at least one divalent
chain which forms, together with two carbon atoms of the substituted ring,
at least one 3- to 7-membered saturated or unsaturated hydrocarbon ring
structure. The alkyl group, the alkoxy group, or the alkyl ester group
represented by R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8, or the
cyclic hydrocarbon chain formed therefrom may optionally have a bond
giving rise to a carbonyl, ether, ester, amide, sulfide, sulfinyl,
sulfonyl or imino.
Specific examples of the basic skeleton for the condensed heteropolycyclic
compound represented by formula (VI) include 1,3-dihydroisothianaphthene
(a compound where in formula (VI), r is 0, and X.sup.1, X.sup.2, X.sup.3
and X.sup.4 each is H), 1,3-dichloroisothianaphthene (a compound where in
formula (VI), r is 0, X.sup.1 and X.sup.3 each is Cl, and X.sup.2 and
X.sup.4 each is H), 1,1,3,3-tetrachloroisothianaphthene (a compound where
in formula (VI), r is 0 and X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each is
Cl), 1,3-dihydronaphtho[1,2-c]thiophene (a compound where in formula (VI),
r is 1, and X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each is H),
1,3-dihydronaphtho[2,3-c]thiophene (a compound where in formula (VI), r is
1 and X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each is H),
1,3-dichloronaphtho[2,3-c]thiophene (a compound where in formula (VI), r
is 1 and X.sup.1 and X.sup.3 each is Cl, and X.sup.2 and X.sup.4 each is
H), 1,3-dihydroanthra[1,2-c]thiophene (a compound where in formula (VI), r
is 2, and X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each is H),
1,3-dihydroanthra[2,3-c]thiophene (a compound where in formula (VI), r is
2, and X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each is H), 1,3
-dihydrophenanthra[1,2-c]thiophene (a compound where in formula (VI), r is
2, and X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each is H),
1,3-dihydrophenanthra[2,3-c]thiophene (a compound where in formula (VI), r
is 2, and X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each is H),
1,3-dihydrophenanthra[3,4-c]thiophene (a compound where in formula (VI), r
is 2 and X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each is H),
1,3-dihydrophenanthra[9,10-c]thiophene (a compound where in formula (VI),
r is 2 and X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each is H),
1,3-dihydronaphthaceno[1,2-c]thiophene (a compound where in formula (VI),
r is 3 and X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each is H), and
1,3-dihydronaphthaceno[2,3-c]thiophene (a compound where in formula (VI),
r is 3 and X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each is H), but the
present invention should not be construed as being limited thereto.
Examples of the 3- to 7-membered saturated or unsaturated hydrocarbon
cyclic structures formed by combining the hydrocarbon chain represented by
R.sup.4, R.sup.5, R.sup.6, R.sup.7 or R.sup.8 with each other at an
optional position include 1,3-dihydroperylo[c]thiophene and
1,3-dihydroacenaphtho[c]thiophene structures, but the present invention
should not be construed as being limited thereto.
Further, of the compounds represented by formula (VI), examples of the
condensed heterocyclic compounds containing nitrogen in the condensed ring
include the following compounds, but the present invention should not be
construed as being limited thereto.
##STR11##
Preferred examples of the basic skeleton in the present invention include a
compound having a 1,3-dihydroisothianaphthene structure represented by
formula (X):
##STR12##
wherein R.sup.4, R.sup.5 and R.sup.6 each independently represents a
monovalent group selected from the group consisting of a hydrogen atom, a
linear or branched, saturated or unsaturated alkyl, alkoxy or alkyl ester
group each having from 1 to 20 carbon atoms, preferably from 1 to 12
carbon atoms, SO.sub.3 --M.sup.1, a halogen atom, a nitro group, a cyano
group, a primary, secondary, or tertiary amino group, a trihalomethyl
group, and a substituted or unsubstituted phenyl group, with the proviso
that two or more of R.sup.4, R.sup.5 and R.sup.6 are not SO.sub.3
--M.sup.1 simultaneously, the hydrocarbon chain represented by R.sup.4,
R.sup.5 or R.sup.6 may combine with each other at any optional position to
form at least one divalent chain which forms, together with two carbon
atoms of the substituted ring, at least one 3- to 7-membered saturated or
unsaturated hydrocarbon ring structure, and the alkyl group, the alkoxy
group, or the alkyl ester group represented by R.sup.4, R.sup.5 and
R.sup.6, or the cyclic hydrocarbon chain formed therefrom may optionally
have a bond giving rise to a carbonyl, ether, ester, amide, sulfide,
sulfinyl, sulfonyl or imino; X.sup.1, X.sup.2, X.sup.3 and X.sup.4 each
independently represents a hydrogen atom or a halogen atom; M.sup.1
represents H.sup.+, an alkali metal ion, such as Na.sup.+, Li.sup.+ and
K.sup.+, or a cation of a Vb Group element unsubstituted or substituted
with an alkyl group having from 1 to 30 carbons atoms, preferably from 1
to 20 carbon atoms, more preferably from 1 to 12 carbon atoms, or with an
aryl group having from 6 to 30 carbon atoms, preferably from 6 to 20
carbon atoms, more preferably from 6 to 16 carbon atoms, such as
NH.sub.4.sup.+, NH(CH.sub.3).sub.3.sup.+, N(CH.sub.3).sub.4.sup.+,
NH(C.sub.2 H.sub.5).sub.3.sup.+, N(C.sub.6 H.sub.5).sub.4.sup.+,
PH.sub.4.sup.+, P(CH.sub.3).sub.4.sup.+, P(C.sub.6 H.sub.5).sub.4.sup.+,
AsH.sub.4.sup.+, As(CH.sub.3).sub.4.sup.+ and As(C.sub.6
H.sub.5).sub.4.sup.+, and a compound having a
1,3-dihydronaphtho[2,3-c]thiophene structure represented by formula (XI):
##STR13##
wherein R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, X.sup.1, X.sup.2,
X.sup.3, X.sup.4 and M.sup.1 each has the same meaning as in formula (VI).
Useful examples of the substituents R.sup.4, R.sup.5, R.sup.6, R.sup.7 and
R.sup.8 in formulae (VI), (VII), (VIII) and (XI), and the substituents
R.sup.4, R.sup.5 and R.sup.6 in formulae (IX) and (X) include a hydrogen
atom, a halogen atom, SO.sub.3 --M.sup.1, a saturated alkyl group, an
unsaturated alkyl group, a saturated alkoxy group, an unsaturated alkoxy
group, a saturated alkyl ester group, an unsaturated alkyl ester group, a
nitro group, and a cyano group. More specific examples of the substituents
include chlorine, bromine, fluorine and iodine as a halogen atom, methyl,
ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl, octyl, dodecyl,
tetradecyl, methoxyethyl, ethoxyethyl, (2-methoxy)ethyl, acetonyl, vinyl,
1-methylethenyl, 2-methylethenyl, crotonyl, allyl, phenyl, tolyl, xylyl,
and phenacyl as the hydrocarbon chain of the saturated or unsaturated
alkyl or alkyl ester group, and methoxy, ethoxy, (2-methoxy)ethoxy,
propoxy, isopropoxy, hexyloxy, octyloxy, and dodecyloxy as the alkoxy
group.
In addition to the foregoing, examples of the substituents include an amino
group, such as methylamino, ethylamino, diphenylamino, and anilino, and a
group, such as trifluoromethyl, chlorophenyl, and acetamide.
Useful examples of the substituents X.sup.1, X.sup.2, X.sup.3 and X.sup.4
in formulae (VI), (X) and (XI) include hydrogen, fluorine, chlorine,
bromine, and iodine.
More specific examples of the compounds represented by formula (X) include
1,3-dihydroisothianaphthene-5-sulfonic acid,
1,3-dichloroisothianaphthene-5-sulfonic acid,
1,3-dibromoisothianaphthene-5-sulfonic acid,
1,1,3,3-tetrachloroisothianaphthene-5-sulfonic acid,
1,3-dihydro-6-methoxyisothianaphthene-5-sulfonic acid,
1,3-dichloro-6-methoxyisothianaphthene-5-sulfonic acid,
1,3-dihydro-6-butoxyisothianaphthene-5-sulfonic acid,
1,3-dihydro-6-decyloxyisothianaphthene-5-sulfonic acid,
1,3-dihydro-6-methoxycarbonylisothianaphthene-5-sulfonic acid,
1,3-dihydro-4,7-dimethoxyisothianaphthene-5-sulfonic acid,
1,3-dihydroisothianaphthene-5,6-disulfonic acid,
1,3-dibromo-4,7-dimethoxyisothianaphthene -5-sulfonic acid,
1,3-dihydro-5,6-dioxymethyleneisothianaphthene-4-sulfonic acid,
1,3-dihydro-6-nitroisothianaphthene-5-sulfonic acid,
1,3-dihydro-6-bromoisothianaphthene-5-sulfonic acid,
1,3-dihydro-6-cyanoisothianaphthene-5-sulfonic acid,
1,3-dihydro-6-aminoisothianaphthene-5-sulfonic acid,
1,3-dihydro-6-trifluoromethylisothianaphthene-5-sulfonic acid, and a
lithium salt, a sodium salt, a potassium salt, an ammonium salt, and a
quaternary ammonium salt of these sulfonic acid derivatives, but the
present invention should not be construed as being limited thereto.
More specific examples of the compounds represented by formula (XI) include
1,3-dihydronaphtho[2,3-c]thiophene-5-sulfonic acid,
1,3-dichloronaphtho[2,3-c]thiophene-5-sulfonic acid,
1,3-dibromonaphtho[2,3-c]thiophene-5-sulfonic acid,
1,3-dihydronaphtho[2,3-c]thiophene-6-sulfonic acid,
1,1,3,3-tetrachloronaphtho[2,3-c]thiophene-5-sulfonic acid,
1,3-dihydro-7-methoxynaphtho[2,3-c]thiophene-6-sulfonic acid,
1,3-dihydro-5,7-dimethoxynaphtho[2,3-c]thiophene-6-sulfonic acid,
1,3-dibromo-5,7-dimethoxynaphtho[2,3-c]thiophene-6-sulfonic acid,
1,3-dihydro-6,7-dioxymethylenenaphtho[2,3-c]thiophene 5-sulfonic acid,
1,3-dihydro-8-methoxycarbonylnaphtho[2,3-c]thiophene-6-sulfonic acid,
1,3-dihydro-7-nitronaphtho[2,3-c]thiophene-5-sulfonic acid,
7-bromo-1,3-dihydronaphtho[2,3-c]thiophene-5-sulfonic acid,
7-cyano-1,3-dihydronaphtho-[2,3-c]thiophene-5-sulfonic acid,
1,3-dihydro-7-methylnaphtho[2,3-c]thiophene-6-sulfonic acid,
1,3-dihydro-6,7-dimethylnaphtho[2,3-c]thiophene-5-sulfonic acid,
1,3-dihydro-7-trifluoromethylnaphtho[2,3-c]thiophene-5-sulfonic acid, and
a lithium salt, a sodium salt, a potassium salt, an ammonium salt, and a
quaternary ammonium salt of these sulfonic acid derivatives, but the
present invention should not be construed as being limited thereto.
In the compound represented by formula (VI), (X) or (XI), the
electroconductive polymer comprising at least one structural unit
represented by formula (VII), and the electroconductive polymer comprising
a structure represented by formula (VIII) or (IX), the counter cation of
the sulfonic acid ion is H.sup.+, an alkali metal ion, such as Na.sup.+,
Li.sup.+ and K.sup.+, or a cation of a Vb Group element unsubstituted or
substituted with an alkyl group having from 1 to 30 carbon atoms,
preferably from 1 to 20 carbon atoms, more preferably from 1 to 12 carbon
atoms, or with an aryl group having from 6 to 30 carbon atoms, preferably
from 6 to 20 carbon atoms, more preferably from 6 to 16 carbon atoms, such
as NH.sub.4.sup.+, NH(CH.sub.3).sub.3.sup.+, N(CH.sub.3).sub.4.sup.+,
NH(C.sub.2 H.sub.5).sub.3.sup.+, N(C.sub.6 H.sub.5).sub.4.sup.+,
PH.sub.4.sup.+, P(CH.sub.3).sub.4.sup.+, P(C.sub.6 H.sub.5).sub.4.sup.30 ,
AsH.sub.4.sup.+, As(CH.sub.3).sub.4.sup.+ and As(C.sub.6
H.sub.5).sub.4.sup.+. In these formulae, M.sup.1 may be a plurality of
different cations selected from the above-described cations. The
conversion into a specific cation may be conducted by ion exchange into a
desired cation by using a conventional ion-exchange resin or a dialysis
membrane.
X.sup.1, X.sup.2, X.sup.3 and X.sup.4 in formulae (VI), (X) and (XI) each
independently represents a hydrogen atom or a halogen atom. The halogen is
preferably chlorine, bromine or iodine, and more preferably chlorine or
bromine.
When the cation represented by M.sup.1 is H.sup.+, the electroconductive
polymer having a main chain of a .pi.-electron conjugated structure and
comprising a chemical structure represented by formula (VII), (VIII) or
(IX) exhibits a self-doping state in an aqueous solution without the help
of an external dopant, and in particular, may exhibit a gel state at a
high concentration. Further, by changing the cation represented by
M.sup.1, the solubility in various solvents, or the affinity to the
solvent, can be varied.
The electroconductive copolymer comprising a chemical structure represented
by formula (VIII) according to this embodiment of the present invention is
a copolymer comprising at least one structural unit represented by formula
(VII) as a repeating unit and another repeating unit of a .pi.-electron
conjugated structure in the main chain structure of the polymer. Examples
of the repeating unit of the .pi.-electron conjugated structure include
vinylene, an aromatic structure and a heterocyclic structure. Examples of
the aromatic structure and the heterocyclic structure include
isothianaphthenylene, isobenzofurylene, isobenzoindolylene,
isobenzoselenylene, isobenzotellurylene, thienylene, pyrrolylene,
furylene, selenylene, tellurylene, iminophenylene and phenylene
structures. A plurality of these skeleton structures may be present.
Further, the repeating unit of the above-described .pi.-electron
conjugated structure may be substituted with a substituent which does not
inhibit the polymerization. Suitable substituents include any of those
described above for R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8.
In the electroconductive copolymer comprising a chemical structure
represented by formula (VIII), p and q represent the molar fractions of
the respective repeating units in the copolymer as described above.
Accordingly, p and q of formula (VIII) do not denote a block copolymer.
With respect to the molar fractions of the above-described copolymer (p:q,
with the proviso that p+q=1), p as the molar fraction of the repeating
unit composed of the structural unit represented by formula (VII) is
preferably from 0.05 to 0.95, more preferably from 0.2 to 0.9 and most
preferably from 0.4 to 0.9. The larger the p value, the greater the water
solubility.
The molecular weight of the water-soluble electroconductive polymer of the
present invention of the formula (I), (II) and (III), is in the range
between 1,000 and 500,000, preferably between 10,000 and 100,000.
Moreover, the polymer comprising at least one structural unit represented
by formula (VII) as a repeating unit and the copolymer comprising a
chemical Structure represented by formula (VIII) or (IX) have a molecular
weight of from 1,000 to 500,000, preferably from 10,000 to 100,000.
A process for producing an electroconductive polymer comprising a chemical
structure represented by formula (VII) or an electroconductive copolymer
comprising a chemical structure represented by formula (VIII) or (IX)
comprises the homopolymerization or copolymerization of the compound
having a chemical structure represented by formula (VI), (X) or (XI), or
the above-described compound and another aromatic compound, and/or
heterocyclic compound, and/or compound capable of forming .pi.-electron
conjugated structure.
The compound having a chemical structure represented by formula (VI), (X)
or (XI) can be polymerized alone or in the presence of another aromatic
and/or heterocyclic compounds of a .pi.-electron conjugated structure
and/or a compound capable of forming a .pi.-electron conjugated structure,
under an elevated temperature or at room temperature or at a low
temperature or while raising the temperature, favored by the action of the
oxidizing agent employed. Accordingly, the polymer comprising a chemical
structure represented by formula (VII) or the copolymer comprising a
chemical structure represented by formula (VIII) or (IX) can be produced
very efficiently.
In particular, when the compound having a chemical structure represented by
formula (VI), (X) or (XI) is subjected to the polymerization reaction at a
high temperature where a sulfonic acid group is readily released, a
copolymer comprising a chemical structure represented by formula (VIII) or
(IX) is obtained.
Examples of the oxidizing agent which brings about an oxidative
dehydrogenation reaction in the polymerization generally include a
sulfonating reagent, such as sulfuric acid, fuming sulfuric acid, sulfur
trioxide, chlorosulfuric acid, fluorosulfuric acid and amidosulfuric acid,
and an oxygen-oxidizing agent using ozone, a peroxide, a peracid, a
quinone, such as 2,3-dichloro-5,6-dicyano-1,4-benzoquinone,
tetrachloro-1,2-benzoquinone, tetrachloro-1,4-benzoquinone, and
tetracyano-1,4-benzoquinone, halogen, such as iodine and bromine,
anhydrous aluminum chloride/copper(I) chloride, anhydrous iron(III)
chloride, a vanadium-, manganese- or nickel-based metal complex, and a
combination of these oxidizing agents. However, there is no particular
restriction on the oxidizing agent.
The addition amount of the oxidizing agent varies depending upon the
compound having a chemical structure represented by formula (VI), (X) or
(XI), and the kind of the oxidizing agent used, and cannot be absolutely
determined. However, in general, the oxidizing agent is preferably used in
an amount of from 1.1- to 20-fold equivalent, more preferably from 2- to
5-fold equivalent, of the compound.
The concentration of the compound having a chemical structure represented
by formula (VI), (X) or (XI) used in the process of the present invention
varies depending upon the kind of the compound, the reaction scale, and
the kind of chemical compound, such as solvent and/or the absence or
presence thereof. However, in general, the concentration of the compound
is preferably from 10.sup.-3 to 10 mol/liter, more preferably from
10.sup.-2 to 1 mol/liter.
The reaction temperature is determined according to the reaction method
employed, and cannot be specifically restricted. However, in general, the
reaction temperature is preferably from -70.degree. C. to 250.degree. C.,
more preferably from 0.degree. C. to 150.degree. C. Further, although the
chemical structure never imposes any restriction on the reaction
temperature, it is preferably 70.degree. C. or higher when a copolymer
comprising a chemical structure represented by formula (VIII) or (IX) is
produced using only a compound having a chemical structure represented by
formula (VI), (X) or (XI).
The reaction time varies depending upon the reaction method, the reaction
temperature, the reaction pressure, or the chemical structure of the
compound and cannot be absolutely defined. However, in general, it
preferably from 0.01 hour to 240 hours, more preferably from 0.1 hour to
24 hours. The reaction pressure is preferably a normal pressure, but may
be from 10.sup.-5 to 100 atm, and more preferably from 1 to 10 atm.
The substitution ratio of the sulfonic acid group of the repeating units in
the polymer can be decreased by raising the temperature during the
reaction up to 60.degree. to 150.degree. C., for 10 min to 20 hours,
preferably up to 80.degree. to 120.degree. C., for 30 min to 10 hours.
The reaction solvent, which is used if desired, varies depending upon the
reaction temperature, the reaction time, the oxidizing agent and the
chemical structure of the compound used, and cannot be absolutely
determined. However, any solvent may be used as long as the solvent
dissolves the compound or the oxidizing agent, and does not inhibit the
polymerization reaction. Specific examples of the solvent include water,
sulfuric acid, fuming sulfuric acid, formic acid, acetic acid, propionic
acid, acetic anhydride, an ether, such as tetrahydrofuran, dioxane and
diethyl ether, a polar solvent, such as dimethylformamide, acetonitrile,
benzonitrile, N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO), an
ester, such as ethyl acetate and butyl acetate, and a non-aromatic
chlorine-based solvent, such as chloroform and methylene chloride. A mixed
solvent of these solvents may also be used.
The thus produced polymer comprising at least one structural unit
represented by formula (VII) as a repeating unit or copolymer comprising a
chemical structure represented by formula (VIII) or (IX) exhibits high
solubility in the solvent, and also has a water solubility due to the
sulfonic acid group. Because of these characteristics, the polymer or
copolymer can be isolated and purified through ultrafiltration, dialysis
and/or ion-exchange operations. In the case when the polymer comprising a
chemical structure represented by formula (VII) or the copolymer
comprising the chemical structure represented by formula (VIII) or (IX) is
obtained as a precipitant from the reaction solvent, the polymer or the
copolymer can be isolated and purified through filtration, reprecipitation
and/or solvent fractionation.
The copolymer comprising the chemical structure represented by formula
(VIII) or (IX) is produced by polymerizing the compound represented by
formula (VI), (X) or (XI) in the presence or with the sequential addition
of another aromatic and/or heterocyclic compound of a .pi.-electron
conjugated structure, and/or a compound capable of forming a n-conjugated
structure after the reaction.
Examples of the aromatic compound and the heterocyclic compound used herein
include isothianaphthene, isobenzofuran, isobenzoindoline,
isobenzoselenaphene, isobenzoterenaphene, thiophene, pyrrole, furan,
selenophene, tellurophene, aniline, benzene, naphtho[2,3-c]thiophene,
anthra[2,3-c]thiophene, naphthaceno[2,3-c]thiophene,
pentaceno[2,3-c]thiophene, perylo[2,3-c]thiophene,
acenaphtho[2,3-c]thiophene and their derivatives having various
substituents. Suitable substituents include any of those described above
for R.sup.4, R.sup.5, R.sup.6, R.sup.7 and R.sup.8.
Examples of the compound capable of forming a conjugated structure after
the reaction include a 1,3-dihydro form, a 1,3-dihalogeno form, a
1,1,3,3-tetrahalogeno form and a 2-oxide form of the above-described
isothianaphthene, 5-alkoxyisothianaphthene, 5,6-dialkoxyisothianaphthene,
naphtho[2,3-c]thiophene, anthra[2,3-c]thiophene,
naphthaceno[2,3-c]thiophene, pentaceno[2,3-c]thiophene,
perylo[2,3-c]thiophene, and acenaphtho[2,3-c]thiophene.
A compound containing nitrogen in the condensed ring may also be used, and
examples thereof include 1,3-dihydrothieno[c]pyridine,
1,3-dihydrothieno[c]pyrazine, 1,3-dihydrothieno[c]pyridazine and
1,3-dihydro-thieno[c]quinoxaline. Of these, preferred are compounds which
form a thiophene, isothianaphthene, pyrrole, aniline or
naphtho[c]thiophene structure.
In the process for producing the copolymer according to the present
invention, the content of the sulfonic acid group in the polymer
comprising a chemical structure represented by formula (VIII) or (IX) can
be easily controlled by changing the charging ratio of the compound
represented by formula (VI), (X) or (XI), and the aromatic compound, the
heterocyclic compound or the compound capable of forming a conjugated
structure. Further, the properties of the polymer comprising a chemical
structure represented by formula (VIII) or (IX) can be easily controlled
by changing the kind or ratio of the aromatic compound, the heterocyclic
compound or the compound capable of forming a conjugated structure to be
copolymerized therewith.
The water- and/or organic solvent-soluble electroconductive polymer
obtained by polymerizing the compound having the chemical structure
represented by formula (VI), (X) or (XI) according to the present
invention shows a small energy gap as a semiconductor, and a high
conductivity at a low doping level as compared with known
electroconductive polymers, for example, a polythiophene derivative
(disclosed in JP-A-2-242816), and has been found to be very stable in its
electroconductive state. Further, due to the effect of the sulfonic acid
group as a substituent, a self-doping state readily arises.
In the present invention, an electroconductive polymer comprising a
chemical structure represented by formula (VII) or (VIII) can be very
efficiently produced by reacting an oxidizing agent with the condensed
heteropolycyclic compound having a sulfonic acid group represented by
formula (VI). The condensed heteropolycyclic compound of a .pi.-electron
conjugated system, such as isothianaphthene and naphtho[c]thiophene, is
very highly reactive and hard to deal with during production. However, the
sulfonic acid group-containing 1,3-dihydroheteropolycyclic compound
represented by formula (VI) is very stable and can be easily handled in
respective unit operations for producing the compound. In other words, the
present invention makes it feasible to produce a sulfonic acid
group-containing electroconductive polymer or copolymer by the
polymerization of a sulfonic acid group-substituted condensed
heteropolycyclic compound having a 1,3-dihydro structure as a monomer.
Among those polymers having a chemical structure represented by any of the
formula (I), (II) and (III), a polyisothianaphthene derivative (i.e., S
for X in the formula (I), (II) or (III) has such a small energy gap as
about 1.0 eV as a semiconductor, which is smaller than that of a known
water-soluble electroconductive polymer such as a polythiophene derivative
having a sulfoalkyl group as a substituent, and is characterized by
exhibiting high conductivity at a low doping level and having high
stability in its conductivity. Therefore, the present polymer has
sufficiently weak absorbance in the visible ray region, particularly in a
doped state, so that it can serve as a transparent conducting material
having high stability in its conductivity.
The process for producing a polymer according to the present invention
provides a practical and novel bicyclic water-soluble electroconductive
polymer by reacting a sulfonating agent with a compound represented by the
formula (IV) or formula (V). This process using the sulfonating agent
provides the novel bicyclic water-soluble electroconductive polymer from a
relevant monomer by simultaneously effecting the polymerization reaction
and the sulfonating reaction in one step. Thus, it constitutes itself a
novel method of production. Namely, the process of the present invention
for producing compounds represented by the formulas (I), (II) and (III) is
a particularly effective means for producing the bicyclic water-soluble
electroconductive polymer from said monomer compound by said reactions
effected in one step. This advantage is well appreciated because such a
bicyclic electroconductive polymer as polyisothianaphthene is infusible
and insoluble in organic solvents or in Bronsted acid such as mineral
acids and accordingly, the sulfonation does not proceed like polyaniline
which is soluble in organic solvents.
The water-soluble electroconductive polymer having a chemical structure
represented by the formula (I) produces an amphoteric water-soluble
electroconductive polymer having a chemical structure represented by the
formula (II) and/or (III) by electrochemical or chemical oxidation.
Conversely, the polymer having a chemical structure represented by the
formula (II) and/or (III) converts itself into a polymer having a chemical
structure represented by the formula (I) by electrochemical or chemical
reduction. Thus, the polymer having a chemical structure represented by
the formula (I) and the polymer having a chemical structure represented by
the formula (II) and/or (III) can be reversibly doped and de-doped by an
oxidation/reduction reaction.
The doping mentioned above can be effected by any of the known
electrochemical and chemical methods. For example, electrochemical doping
method which comprises nipping a water-soluble electroconductive polymer
film between opposed electrodes, placing the nipped film in a solution
containing a dopant, and applying a potential to the electrodes may be
adopted. For chemical doping, the gaseous phase method which comprises
causing a dopant such as iodine in the gaseous phase to react on a
water-soluble electroconductive polymer film may be used (See "Fundamental
Principles and Applications of Conducting Polymers--Synthesis, Physical
Properties, Evaluation, and Applied Technologies", page 245-259, I.P.C.).
The dopants which are effectively usable in the reaction under discussion
(represented by the symbol Z in the formula (III)) include halogenide
anions of Vb group elements such as PF.sub.6.sup.-, AsF.sub.6.sup.- and
SbF.sup.6-, halogenide anions of IIIb group elements such as
BF.sub.4.sup.-, halogen anions such as I.sup.- (I.sub.3.sup.-), Br.sup.-
and Cl.sup.-, perhalogenate anions such as ClO.sub.4.sup.-, Lewis acid,
protonic acid, electrolytic anions and polyelectrolytic anions, for
example. The dopant does not need to be limited to these examples.
Optionally, two or more such dopants may be used in combination.
Now, the process to be employed in producing the water-soluble
electroconductive polymer of the present invention of the formula (I),
(II) and/or (III) will be described below.
The polymer having a chemical structure represented by the formula (I),
(II) and/or (III) can be produced by reacting a sulfonating agent such as
fuming sulfuric acid with the compound having the formula (IV) or (V).
Specifically, the reaction of cationic polymerization and the reaction of
sulfonation occur in one and the same reaction solution on the compound
represented by the formula (IV) or (V) to produce the polymer having a
chemical structure represented by the formula (II) or (III). The produced
polymer can be easily converted by neutralization into the polymer having
a chemical structure represented by the formula (I). The polymer having
structure (II) or (III), therefore, may be utilized in its unmodified
form. Since the control of the doping level in the compound (II) or (III)
is easy to effect, it will be more convenient to produce the polymer
having structure (I) by thoroughly effecting the neutralization mentioned
above and, whenever necessary, produce the polymer having structure (II)
or (III) from the polymer having structure (I) as mentioned above.
Of the compounds represented by the General formula (IV), those compounds
having H for both R.sup.1 and R.sup.2 and S for Y can be easily produced
by such known methods as disclosed by J. A. Gladysz et al. in Tetrahedron,
35, 2329 (1979), for example.
Of the compounds having the formula (V), those compounds having H for both
R.sup.1 and R.sup.2 and S for X can be easily produced from the compounds
having the formula (IV) by such known methods as disclosed by R. Meyer et
al. in J. Prakt. Chem., 20, 244 (1963), for example.
The sulfonating agents which are effectively usable herein include, for
example, sulfuric acid, fuming sulfuric acid, sulfur trioxide,
chlorosulfonic acid, fluorosulfonic acid, and sulfamic acid. Although the
amount of the sulfonating agent to be used herein is not specifically
limited, because it is variable depending the kind of monomer and the kind
of sulfonating agent, the preferable amount is in the range between 1.1 to
20 equivalents to the molar amount of the monomer. Optionally, two or more
such sulfonating agents may be used in combination.
The concentration of the monomer usable in the production of the polymer
having a chemical structure represented by the formula (I), (II), and/or
(III) is generally desired to be in the range between 10.sup.-4 and 10
mol/liter, although it is variable depending upon the kind of monomer and
the scale of reaction.
The reaction temperature usable in the production of the polymer having a
chemical structure represented by the formula (I), (II), and/or (III) is
not particularly limited but fixed, depending on the particular method of
reaction to be used. Generally, the reaction temperature is preferably in
the range between -80.degree. C. and 250.degree. C., more preferably
between -30.degree. C. and 150.degree. C. The polymerization time is
preferably in the range between 0.01 hour and 200 hours, although it is
variable depending upon the method of polymerization, the temperature of
polymerization or the monomer and cannot be generally defined.
The solvent usable in the polymerization reaction for the production of the
polymer having a chemical structure represented by the formula (I), (II),
and/or (III) from the compound having the formula (IV) or (V) cannot be
generally defined because it is variable, similarly to the polymerization
temperature and the polymerization time, depending upon the sulfonating
agent and the monomer to be used in the polymerization reaction. The
solvent is only required to be capable of dissolving the monomer and the
sulfonating agent and to be one inhibiting neither the reaction of
sulfonation nor the polymerization reaction. More specifically, the
solvents which are effectively usable herein include, for example, water,
sulfuric acid, fuming sulfuric acid, formic acid, acetic acid, propionic
acid, acetic anhydride, ethers such as tetrahydrofuran, dioxane and
diethyl ether, polar solvents such as dimethyl formamide, acetonitrile and
benzonitrile, esters such as ethyl acetate and butyl acetate, and
non-aromatic chlorine type solvents such as chloroform and methylene
chloride. Optionally, these solvents may be used in the form of any
mixture thereof.
Further, in order to prevent the formation of sulfone compound as a
by-product which is known to be formed during the reaction of sulfonation,
any known inhibitory compound may be added upon and during the sulfonation
and polymerization reactions. Although the inhibitory compound to be used
herein and its amount are variable depending upon the sulfonating agent
and monomer, specific examples of such compounds include fatty acids,
organic peroxides, fatty acid anhydrides, pyridine, acetic acid, ketones
and the like, effectively usable in the range between 0.01 and 5 mole %.
The polymer having a chemical structure of the formula (I), (II), or (III)
is soluble in water and may include one which is also soluble in organic
solvents. In the case of the polymer which is prepared in the form of an
aqueous solution, it can be separated and purified by ultrafiltration,
dialysis, and/or ion exchange operation. In the case of the polymer which
is prepared in the form of precipitate from the solvent used in the
reaction, it can be separated and purified by filtration, reprecipitation,
and/or solvent fractionation.
The polymer according to the present invention may be a copolymer with
another monomer which is capable of imparting to the copolymer a
main-chain structure possessing a .pi.-electron conjugate system, or a
copolymer which contains, for example, isothianaphthenylene,
isobenzofurylene, isobenzoindolylene, isobenzoselenylene,
isobenzoterullylene, thienylene, pyrrolylene, furylene, selenylene,
terullylene, iminophenylene, phenylene, vinylene and/or ethynylene
structures in the polymer main chain. It should be noted that the
copolymers are not limited to these examples. The copolymer can be
produced by allowing such a heterocyclic monomer as one which generates
the main-chain structure as mentioned above to coexist in the reaction
mixture of polymerization reaction described herein.
When such a heterocyclic monomer as one which produces the main-chain
structure as mentioned above is copolymerized by the method described
above with the compound having the formula (IV) or (V), the product of
this copolymerization is a polymer containing one structure having the
formula (I), (II), and/or (III) or a polymer containing two or more such
structures. The polymers, including copolymers, having the chemical
structure represented by the formula (I), (II) and/or (III) and obtained
by the above-mentioned production method generally exhibit high degrees of
solubility in water. When the symbol M in the general formula is hydrogen,
some of the polymers produced assume the form of gel in a high
concentration. The solubility in a solvent and the affinity to the solvent
of the polymers may be varied depending upon the symbol M.
From the polymers having the chemical structure represented by the formula
(I), (II), or (III) or copolymers thereof, owing to their solubility in
water, films, linear shaped articles such as fibers, or bulky shaped
articles such as rods, plates, sheets and other solid articles can be
easily manufactured by the molding or film making methods which are known
in the plastic industry.
The concentration of the solution to be used in said molding or film making
methods is preferably in the range between 0.5% and 60% by weight,
although it is variable depending upon the condition of molding, the
chemical structure of polymer, or the kind of solvent. The molding or film
making process is preferably carried out in an atmosphere of inert gas or
under vacuum. A film of the polymer can be produced by preparing a
solution of the polymer in an appropriate solvent and casting the polymer
in an appropriate solvent and casting the polymer solution on a proper
medium such as, for example, a glass plate or sodium bromide disc. Fibers
or a bulky shaped article of the polymer is produced by directly shaping
the polymer solution in a desired shape. The polymer, when necessary, may
be stretched to a desired shape.
Furthermore, according to the present invention, the water-soluble
conducting polymer can be processed to similar articles as above which
comprise such a water-soluble conducting polymer and another polymer such
as polyvinylalcohol in an optional ratio, for example, by dissolving or
mixing the former and the latter in an appropriate solvent and processing
the polymers contained in the resulting solution (or the mixture) into a
desired shaped article by a similar method as above. In such a case, the
amount of said another polymer may preferably be used in the range between
10 and 500% by weight of the water-soluble conducting polymer. The solvent
used herein is preferably water, but is not limited to water and may be
selected from any other solvents or may be a mixed solvent, provided that
the polymer has sufficient solubility in such a selected solvent for
processing a shaped article.
The shaped articles manufactured by the above-mentioned processes have
quite stable conductivity during the long period of time.
The present invention is based on the principle that the novel
water-soluble electroconductive polymer having a chemical structure
represented by the formula (I) can be obtained by reacting a sulfonating
agent with the bicyclic heterocyclic monomer compound having the formula
(IV) or (V). The polymer is obtained, for the first time, solely by the
particular reaction in which the reaction of sulfonation and the
polymerization reaction are simultaneously effected by directly reacting
the sulfonating agent on the monomer compound.
The polymer having the chemical structure represented by the formula (I)
converts itself into the water-soluble electroconductive polymer having
the chemical structure represented by the formula (II) or (III) by doping,
thereby the conductivity of the polymer is remarkably increased. This
novel polymer can be reverted to the original polymer having the chemical
structure represented by the formula (I) by either remarkably increasing
electroconductivity or de-doping.
EXAMPLES
The present invention will now be further illustrated by, but is by no
means limited to, the following Examples.
Example 1
Process for production of the polymer having a chemical structure
represented by the formula (I), having H for both R.sup.1 and R.sup.2, S
for X, and Na.sup.+ for M.
To 2.0 g of fuming sulfuric acid (20% SO.sub.3) kept at 10.degree. C., 550
mg (4.0 mmol) of 1,3-dihydroisothianaphthene, a known compound, was slowly
added as stirred. When the resultant mixture was allowed to cool to a room
temperature and was continued to stir for one hour, the reaction solution
became a reddish purple color. The reaction solution, when heated to
70.degree. C., was changed to a dark blue color. After 30 minutes, it was
turned into a solid substance. The resultant reaction mixture was placed
in 100 ml of 0.1N NaOH/methanol to be neutralized and precipitated
therein. The precipitate was separated with a centrifugal separator. The
solid reaction product was dissolved in 100 ml of water and the resultant
aqueous solution was treated with a dialysis membrane to remove sodium
sulfate as foreign matter. The dialyzed solution was allowed to evaporate
under a reduced pressure to remove the solvent therefrom and then dried
under vacuum, to obtain 430 mg of a black Na form polymer (yield 45%).
The polymer thus produced yielded a UV spectrum illustrated in FIG. 1. The
molecular weight distribution of the polymer measured by GPC is
illustrated in FIG. 2. The IR spectrum of the polymer is illustrated in
FIG. 3. FIG. 4 shows the cyclic voltammogram performed on a polymer film
(polymer film/ITO glass operating electrode, platinum counter electrode,
silver/silver ion reference electrode in acetonitrile, borofluoric
acid-acetonitrile electrolyte, scanning speed 50 mV/sec.). The graph
indicates that the polymer, in a cycle between -0.2 V and +0.7 V under
fixed conditions, can be electrochemically doped and dedoped.
Elementary analyses (%) for C.sub.8 H.sub.3 S.sub.2 O.sub.3 Na
Calculated: C; 41.02%, H; 1.29%, S; 27.38%, Na; 9.82%
Found: C; 40.57%, H; 1.51%, S; 27.55%, Na; 9.38%
Example 2
Process for production of the polymer having a chemical structure
represented by the formula (I) having H for both R.sup.1 and R.sup.2, S
for X, and H.sup.+ for M.
An aqueous solution was prepared by dissolving 380 mg of a reaction mixture
obtained in the same manner as in Example 1 in about 1,000 ml of water and
adjusting a pH of the solution to 1.9 with hydrochloric acid. The aqueous
solution was purified and concentrated by ultrafiltration. The concentrate
was allowed to evaporate under a reduced pressure to remove water and
dried under vacuum, to obtain 320 mg of a black polymer.
The UV spectrum of the polymer produced above is illustrated in FIG. 5.
When the polymer was then adjusted to a pH value of about 8 by addition of
aqueous NaOH, the UV spectrum of the polymer in the solution was changed
to that which is illustrated in FIG. 1.
Example 3
Process for production of the polymer having a chemical structure
represented by the formula (I) having H for both R.sup.1 and R.sup.2, S
for X, and H.sup.+ for M.
An aqueous solution of acid form polymer was obtained by dissolving 200 mg
of a polymer prepared in the same manner as in Example 1 in 50 ml of water
and subjecting the resultant solution to an ion-exchange treatment using
an H form cation-exchange resin (Amberlite IR-120B). When this aqueous
solution was allowed to evaporate under a reduced pressure to remove water
and dried under vacuum, 180 mg of a black polymer was obtained. The
spectrum of the produced polymer was similar to that shown in FIG. 5.
Example 4
Process for production of the polymer having a chemical structure
represented by the formula (I) having H for both R.sup.1 and R.sup.2, S
for X, and H.sup.+ for M.
In 4.0 ml of sulfuric acid containing 2.0 ml of fuming sulfuric acid (20%
SO.sub.3), 500 mg of 1,3-dihydroisothianaphthene was slowly added as
stirred at a room temperature and then continuously stirred overnight. The
resultant reaction solution exhibited a red color. When it was then heated
to 90.degree. C., it changed a dark blue color at once. After three hours,
it was turned into a dark blue homogeneous solution.
Further, the reaction mixture was heated and stirred at the same
temperature for two hours and then poured into 1,000 ml of water. The
resultant aqueous solution was adjusted to pH 1.9, purified with an
ultrafilter membrane and concentrated to 100 ml. The concentrate was
allowed to evaporate under a reduced pressure to remove water and dried
under vacuum, to obtain 390 mg of a black polymer.
The UV spectrum and the IR spectrum of the polymer produced above were
similar to those obtained in Example 2.
Elementary analysis (%) for C.sub.8 H.sub.4 O.sub.1.65 S.sub.1.55
Calculated: C; 54.54%, H; 2.27%, S; 28.18%
Found: C; 55.33%, H; 2.98%, S; 27.45%
Example 5
Process for production of the polymer having a chemical structure
represented by the formula (I) having H for both R.sup.1 and R.sup.2, S
for X, and Na.sup.+ for M.
To 2.0 g of fuming sulfuric acid (20% SO.sub.3) kept at 10.degree. C., 500
mg (4.0 mmol) of 1,3-dihydroisothianaphthene-2-sulfoxide, a known
compound, was slowly added as stirred. The resultant mixture was allowed
to cool to room temperature and stirred continuously for one hour. The
reaction solution exhibited a reddish purple color. When the reaction
solution was then heated to 80.degree. C., it changed to a dark blue
color. After 30 minutes, it was turned into a solid substance. The
resultant reaction mixture was placed in 100 ml of 0.1N NaOH/methanol. The
precipitate was dissolved in 100 ml Of water, dialyzed to expel excess
sodium sulfate, then the dialyzed solution was allowed to evaporate under
a reduced pressure to remove the solvent, and dried under a vacuum to
obtain 430 mg of a black polymer.
The UV spectrum and the IR spectrum of the produced polymer were similar to
those obtained in Example 1.
Elemental analyses (%) for C.sub.8 H.sub.2.88 O.sub.3.36 S.sub.1.12
Na.sub.1.12
Calculated: C; 44.81%, H; 1.34%, S; 16.73%, Na; 12.02%
Found: C; 44.21%, H; 1.13%, S; 16.53%, Na; 12.84%
Example 6
Process for production of the polymer having a chemical structure
represented by the formula (I) having H for both R.sup.1 and R.sup.2, S
for X, and Na.sup.+ for M.
To 8 ml of sulfuric acid containing 2.0 g of fuming sulfuric acid (20%
SO.sub.3) kept at 0.degree. C. in an atmosphere of nitrogen, 400 mg of
isothianaphthene, a known compound, was slowly added as stirred. When the
resultant mixture was stirred continuously for eight hours, the resultant
reaction solution exhibited a red color. When the reaction solution was
then allowed to cool to room temperature and subsequently heated to
90.degree. C., it exhibited a dark blue color. After five hours, it turned
into a homogeneous black solution.
The reaction mixture was poured into 100 ml of 0.1N NaOH/methanol. The
precipitate was centrifugally separated. The solid centrifugate was
dissolved in 100 ml of water, dialyzed to remove excess sodium sulfate,
then the dialyzed solution was allowed to evaporate under a reduced
pressure to remove water, and dried under a vacuum to obtain 220 mg of a
black polymer.
The UV spectrum and the IR spectrum of the produced polymer were similar to
those obtained in Example 1.
Example 7
Conversion of the polymer having a chemical structure represented by the
formula (I) to the polymer having a chemical structure represented by the
formula (II) and/or formula (III).
A polymer film was manufactured by dissolving 50 mg of a polymer prepared
in the same manner as in Example 1 in 2 ml of water and casting the
resultant aqueous solution on an ITO glass plate by spin-casting method.
An electrochemical cell was constructed by using the film-coated ITO glass
plate as a working electrode, a platinum wire as a counter electrode, and
a silver/silver ion electrode as a reference electrode. When a potential
of 0.5 V was applied electrochemically to the cell at a room temperature
in a 0.5 mol/liter HBF.sub.4 /acetonitrile solution (having a water
content of 6%), the film which was in a blue color turned to a grayish
black color.
Example 8
Conversion of the polymer having a chemical structure represented by the
formula (I) to the polymer having a chemical structure represented by the
formula (II) and/or formula (III).
A polymer film was manufactured by dissolving 50 mg of a polymer prepared
in the same manner as in Example 3 in 2 ml of water and casting the
resultant aqueous solution on a platinum foil by spin-casting method. An
electrochemical cell was constructed by using the film-coated platinum
foil as a working electrode, a platinum wire as a counter electrode, and a
silver/silver ion electrode as a reference electrode. When this cell was
electrically scanned at a room temperature in a 0.1 mol/liter
tetrabutylammonium perchlorate/acetonitrile solution, to confirm the
occurrence of the same H.sup.+ -popping as described in "J. Am. Chem.
Soc.", 110, 2983 (1988). The detection of the release of H.sup.+ indicates
that the film possessed a self-doping function. Thus, the production of
the polymer having the chemical structure represented by the formula (II)
was accomplished.
Example 9
Conversion of the polymer having a chemical structure represented by the
formula (I) to the polymer having a chemical structure represented by the
formula (III).
A polymer film was manufactured by dissolving 100 mg of a polymer prepared
in the same manner as in Example 1 in 2 ml of water and casting the
resultant aqueous solution on a glass plate by spin-casting method. When
iodine was allowed to affect this film in a gaseous phase, the color of
the film changed from blue to light blackish gray. The electroconductivity
(determined by four-probe method) at a room temperature rose from
.sigma.=5.times.10.sup.-5 S/cm to .sigma.=8.times.10.sup.-1 S/cm.
Thereafter, the film was separated from the glass plate and subjected to
elementary analysis.
Elementary analyses (%) for C.sub.8 H.sub.3 S.sub.2 O.sub.3 NaI.sub.0.3
Calculated: C; 35.25%, H; 1.10%, S; 23.49%, Na; 8.42%, I; 13.95%
Found: C; 35.47%, H; 1.34%, S; 23.55%, Na; 7.98%, I; 13.74%
Example 10
Process for production of the polymer having a chemical structure
represented by the formula (I) having H for both R.sup.1 and R.sup.2,
NR.sup.3 for X, CH.sub.3 for R.sup.3, and Na.sup.+ for M.
To 4.0 ml of sulfuric acid containing 2.0 ml of fuming sulfuric acid (20%
SO.sub.3), 500 mg of N-methylisoindoline produced by the known method
reported as in Adv. Heterocycl. Chem., 10, 113 (1969) was placed slowly
added as stirred at a room temperature, and stirred continuously for five
hours at a room temperature. When the resultant reaction mixture was then
heated to 90.degree. C. for three hours, the reaction solution exhibited a
black color.
The reaction mixture was poured into 100 ml of methanol. The precipitate
consequently formed was centrifugally separated. The solid centrifugate
was dissolved in 100 ml of 0.5N aqueous sodium hydroxide solution,
dialyzed to remove excess sodium sulfate and sodium hydroxide, then the
dialyzed solution was allowed to evaporate under a reduced pressure to
remove the solvent, and dried under vacuum, to obtain 380 mg of a black
polymer.
IR: (KBr disk, cm.sup.-1); 1803w, 1412w, 1314m, 1225w, 1194s, 1042s, 750s
Example 11
Process for production of the polymer having a chemical structure
represented by the formula (I) having H for R.sup.1, O(CH.sub.2).sub.9
CH.sub.3 for R.sup.2, S for X, and Na.sup.+ for M.
To 8.0 ml of sulfuric acid containing 2.0 ml of fuming sulfuric acid (20%
SO.sub.3) kept at 0.degree. C., 500 mg of
5-decyloxy-1,3-dihydroisothianaphthene produced by a known method as
reported in JP-A-2-242816 was slowly added as stirred and then
continuously stirred for one hour. When the resultant mixture was then
heated to 90.degree. C. for 30 minutes, the reaction solution turned
black.
The resultant reaction mixture was poured into 100 ml of 0.5N aqueous
NaOH/methanol solution and the precipitate was separated centrifugally.
The solid centrifugate consequently obtained was dissolved in 100 ml of
water, dialyzed to remove excess sodium sulfate, then the dialyzed
solution was allowed to evaporate under a reduced pressure to remove the
solvent, and dried under vacuum to obtain 150 mg of a black polymer. The
UV spectrum of the produced polymer was similar to that obtained in
Example 1.
Example 12
On the surface of a glass plate as a support, 10% by weight of an aqueous
solution of a water-soluble conducting polymer prepared in the same manner
as in Example 2 was applied and left drying thereon spontaneously. The
applied layer of the polymer was dried under vacuum and separated from the
glass plate, to obtain a free-standing film of about 20 .mu.m in
thickness. The electroconductivity of this film (determined with d
four-terminal testing system) at a room temperature was .sigma.=1.4 S/cm.
The conductivity of the film remained stable when it was kept in air for
two months.
Example 13
On the surface of a glass plate as a support, an aqueous solution of 1% by
weight of a water-soluble conducting polymer produced in the same manner
as in Example 2 was applied by the use of a spin coater at a 35 room
temperature and a revolution number of 1,000 rpm to form a thin film of
about 0.05 .mu.m in thickness (determined by the needle touch method
called Dektak). This thin film exhibited good adhesiveness to the glass
plate support and showed surface resistance of about 7.8.times.10.sup.5
.OMEGA./.quadrature.. The transmittance of the film at 500 nm in a visible
ray region was 96%. Thus, the polymer yielded a conducting film of
extremely high transparency.
Thin films were prepared in the same manner as above except for the
revolution number of a spin coater and the properties of the films
obtained are 10 shown in Table 1.
TABLE 1
______________________________________
Revolution
Film Surface Transmittance
Numbers Thickness Resistance
(%, at
(rpm) (.mu.m) (.OMEGA./.quadrature.)
500 nm)
______________________________________
200 0.25 1.5 .times. 10.sup.5
83
500 0.10 3.8 .times. 10.sup.5
93
1000 0.05 7.8 .times. 10.sup.5
96
______________________________________
Example 14
On the surface of a glass plate as a support, an aqueous solution
containing 1% by weight of a water-soluble conducting polymer produced in
the same manner as in Example 2 and 1% by weight of polyvinylalcohol
(degree of polymerization of 500) was applied by the use of a spin coater
at a room temperature at a revolution number of 1,000 rpm to form a thin
film of about 1 .mu.m in thickness, determined in the same manner as in
Example 13. This thin film exhibited good adhesiveness to the glass plate
support and showed surface resistance of about 1.times.10.sup.7
.OMEGA./.quadrature.. The transmittance of the film at 500 nm in a visible
ray region was 97%.
Example 15
The water-soluble conducting polymer produced in the same manner as in
Example 2 was not only soluble in water but also in dimethylformamide
(DMF), dimethylsulfoxide (DMSO), N-methylpyrrolidone (NMP) and methanol
respectively.
Example 16
An aqueous solution containing 5% by weight of a water-soluble conducting
polymer produced in the same manner as in Example 10 and 20% by weight of
polyvinylalcohol (degree of polymerization of 2000) was placed in a Petri
dish of a diameter of about 5 cm) and was allowed to evaporate to remove
water and then dried under vacuum. A shaped plate (disc) of about 1 mm in
thickness as formed in the dish was separated from the bottom of the dish.
This shaped article showed surface resistance of about 8.times.10.sup.8
.OMEGA./.quadrature..
Example 17
An aqueous solution containing 10% by weight of a water-soluble conducting
polymer produced in the same manner as in Example 1 and 12% by weight of
polyvinylalcohol (degree of polymerization of 2000) was placed in a
syringe having a muzzle diameter of about 1 mm, and the solution was
slowly extruded into ethanol and kept for a day. A fibrous shaped article
formed was then removed from the solvent, and dried to obtain blackish
blue fiber. The fiber had electroconductivity of .sigma.=2.times.10.sup.-6
S/cm, measured by four-probe method, at a room temperature. When iodine
was allowed to affect this fiber in a gaseous phase in the same manner as
in Example 9, the electroconductivity at a room temperature rose to
.sigma.=5.times.10.sup.-2 S/cm.
This fiber was drawn at a draw ratio of 1.5 at a room temperature, and the
electroconductivity of the resultant fiber rose to 0.3 S/cm.
Example 18
On the surface of a glass plate as a support, an aqueous solution of a
water-soluble conducting polymer produced in the same manner as in Example
2 and polyvinylalcohol (degree of polymerization of 500) as composed at
various ratio was applied by the use of a spin coater at a room
temperature and a revolution number of 1,000 rpm. The surface resistance
of the thin films obtained is shown in Table 2.
TABLE 2
______________________________________
Water-soluble
Conducting Polymer
Polyvinylalcohol
Surface Resistance
______________________________________
1 wt % 1 wt % 1 .times. 10.sup.7 .OMEGA./.quadrature.
1 wt % 5 wt % 3 .times. 10.sup.7 .OMEGA./.quadrature.
1 wt % 10 wt % 3 .times. 10.sup.8 .OMEGA./.quadrature.
______________________________________
Example 19
Production of a compound represented by formula (X), which is a compound
represented by formula (VI) wherein r is 0 (R.sup.4 =R.sup.5 =R.sup.6 =H,
X.sup.1 =X.sup.2 =X.sup.3 =X.sup.4 =H, M.sup.1 =Na.sup.+):
To 4 ml of a fuming sulfuric acid (20% SO.sub.3) cooled to 20.degree. C. or
lower, 1 g of 1,3-dihydroisothianaphthene, which is a known compound, was
gradually added with stirring, followed by stirring for 4 hours at a room
temperature. The reaction mixture was poured into 150 ml of ice water, and
thereto was added 20 g of sodium chloride to salt out sodium
1,3-dihydroisothianaphthene-5-sulfonate, which was then isolated by a
centrifugal separator and vacuum dried to obtain 850 mg of a gray powder
compound.
Example 20
Production of a polymer comprising a chemical structure represented by the
following formula (XII), which is a formula represented by formula (VII)
wherein r is 0 (R.sup.4 =R.sup.5 =R.sup.6 =H, M=H.sup.+):
##STR14##
To a mixed system of 5.5 g of ferric chloride, 1 ml of an aqueous solution
of hydrogen peroxide (30%), and 10 ml of water, 1 g of sodium
1,3-dihydroisothianaphthene-5-sulfonate, produced in the same manner as in
Example 19, was gradually added with stirring. After continuing stirring
one day at a room temperature, a viscous black reaction solution was
obtained.
The reaction mixture was vacuum dried, and then poured into 100 ml of
acetone, and the precipitated polymer was separated by a centrifugal
separator. After drying, the polymer was dissolved in 700 ml of a 0.1N
aqueous NaOH solution, insoluble materials were removed by centrifugation,
and impurities were removed by passing the solution through a 1-.mu.m
filter film. Further, Na.sup.+ ions were converted into H.sup.+ by means
of an H-type ion-exchange resin (Amberlite IR-120B). Water was distilled
off from the aqueous solution, and the residue was vacuum dried to obtain
0.2 g of a blue polymer.
The substitution ratio of the sulfonic acid group of the repeating units in
the polymer was determined by neutralization titration using alkali, and
the polymer was found to consist of almost 100 mol % of the repeating
units having substitution by the sulfonic acid group. The polymer was
subjected to GPC measurement, and found to have a number-average molecular
weight of 18,000 (calculated in terms of sodium polystyrenesulfonate as a
molecular weight standard material).
Example 21
Production of a polymer comprising a chemical structure represented by
formula (IX), which is a formula represented by formula (VIII) wherein r
is 0 (R.sup.4 =R.sup.5 =R.sup.6 =H, M.sup.1 =Na.sup.+, p=0.8, q=0.2,
Ar=1,3-isothianaphthenylene):
To 25 ml of sulfuric acid kept at 10.degree. C. or lower, 1 g of sodium
1,3-dihydroisothianaphthene-5-sulfonate, produced in the same manner as in
Example 19, was gradually added with stirring. After the stirring for 1
hour at room temperature, the reaction solution became reddish violet. The
solution was then heated at 80.degree. C. for 2 hours, and the resulting
black reaction mixture was poured into 60 ml of 0.1N NaOH/MeOH. The
precipitated polymer was isolated by a centrifugal separator, dissolved
into 100 ml of water, and passed through a dialysis membrane to remove
sodium sulfate as an impurity. After distilling off water from the aqueous
solution, the residue was vacuum dried to obtain 0.3 g of a blue polymer.
The visible near infrared absorption spectrum of the resulting polymer is
shown in FIG. 6.
______________________________________
Elemental analysis for (C.sub.8 H.sub.3 S.sub.2 O.sub.3 Na).sub.0.8
(C.sub.8 H.sub.4 S).sub.0.2 :
C H S Na
______________________________________
Calcd. 44.27 2.96 26.59
8.48
Found 44.52 3.23 26.41
8.92
______________________________________
Thereafter, in order to measure the substitution ratio of the sulfonic acid
group of the repeating units in the polymer, 0.2 g of the resulting
polymer was dissolved into water and converted from the Na.sup.+ form to
the H.sup.+ form by means of an H-type ion-exchange resin (Amberlite
IR-120B). After distilling off water from the aqueous solution, the
residue was vacuum dried to obtain 120 mg of a blue polymer.
The substitution ratio of the sulfonic acid group was determined by
neutralization titration, and the polymer was found to be a copolymer
having an average molar fraction of 0.8 of the repeating unit having
sulfonic acid substitution. This reveals that a part of the sulfonic acid
split off during the polymerization reaction.
Example 22
Production of a polymer comprising a chemical structure represented by
formula (IX), which is a formula represented by formula (VIII) wherein r
is 0 (R.sup.4 =R.sup.5 =R.sup.6 =H, M.sup.1 =H.sup.+, P=0.6, 9=0.4,
Ar=1,3-isothianaphthenylene)
To 5 ml of sulfuric acid kept at 10.degree. C. or lower, 0.7 g of sodium
1,3-dihydroisothianaphthene-5-sulfonate, produced in the same manner as in
Example 19, and 0.28 g of 1,3-dihydroisothianaphthene were gradually added
with stirring. After the stirring for 1 hour at room temperature, the
reaction solution turned violet, and when heated at 90.degree. C. for 3
hours thereafter, the reaction solution changed to black. The resulting
reaction mixture was poured into 60 ml of 0.1N NaOH/MeOH, and the
precipitated polymer was isolated by a centrifugal separator. The polymer
was dissolved into 100 ml of water, and passed through a dialysis membrane
to remove sodium sulfate as an impurity. Then, the Na.sup.+ ion was
converted to H.sup.+ by means of an H-type ion-exchange resin (Amberlite
IR-120B). After distilling off water from the aqueous solution, the
residue was vacuum dried to obtain 0.5 g of a blue polymer. The visible
near infrared absorption spectrum of the resulting polymer is shown in
FIG. 7.
The substitution ratio of the sulfonic acid group was determined by
neutralization titration, and the polymer was found to be a copolymer
having an average molar fraction of 0.6 of the repeating unit having
sulfonic acid substitution.
Example 23
Production of a compound represented by formula (XI), which is a compound
represented by formula (VI) wherein r is 1 (R.sup.4 =R.sup.5 =R.sup.6
=R.sup.7 =R.sup.8 =H, X.sup.1 =X.sup.2 =X.sup.3 =X.sup.4 =H, M.sup.1
=Na.sup.+):
Example 19 was repeated except for using 1 g of
1,3-naphtho[2,3-c]thiophene, which is a known compound, in place of
1,3-dihydroisothianaphthene, and sulfonation was carried out on the
resulting solution in the same manner as in Example 19 to obtain 420 mg of
sodium 1,3-naphtho[2,3-c]thiophenesulfonate as a gray powder.
Example 24
Production of a polymer comprising a chemical structure represented by the
following formula (XIII), which is a formula represented by formula (II)
wherein r is 1 (R.sup.4 =R.sup.5 =R.sup.6 =R.sup.7 =R.sup.8 =H, M.sup.1
=NH.sub.4.sup.+):
##STR15##
Example 20 was repeated except for using 700 mg of sodium
1,3-dihydronaphtho[2,3-c]thiophene-6-sulfonate, produced in Example 24, as
a monomer in place of 1,3-dihydroisothianaphthene. Polymerization and
subsequent procedures were conducted in the same manner as in Example 20,
and 200 mg of an acid-form polymer was obtained. The sulfonic acid
substitution ratio of the repeating units thereof was almost 100%. The
polymer was dissolved in water, an excess amount of aqueous ammonium was
added thereto, and the resulting mixture was distilled off under reduced
pressure to obtain a polymer of an ammonium salt. The polymer was again
dissolved in water and its visible near infrared absorption spectrum was
measured. The results are shown in FIG. 8.
Example 25
Production of a compound represented by formula (X), which is a compound
represented by formula (I) wherein r is 0 (R.sup.4 =R.sup.5 =R.sup.6 =H,
X.sup.1 =X.sup.2 =X.sup.3 =X.sup.4 =H, M.sup.1 =(CH.sub.3).sub.3
(n-C.sub.6 H.sub.17)N.sup.+ :
3 g (12.7 mmol) of sodium 1,3-dihydroisothianaphthene-5-sulfonate was
dissolved into 100 ml of purified water while keeping the temperature at
20.degree. C., and thereto was added 3.20 g (12.7 mmol) of
n-octyltrimethylammonium bromide (produced by Tokyo Kasei Co., Ltd. ) with
stirring. After 30 minutes, the mixture was extracted three times with
chloroform (20 ml.times.3 times), and then the chloroform layer was dried
over anhydrous sodium sulfate and distilled off under reduced pressure to
obtain an ion complex form as an oily semisolid (gain: 4.35 g, yield:
89%). The polymer obtained was found to be soluble in chloroform, toluene,
dimethylsulfoxide, tetrahydrofuran and dimethylformamide.
Example 26
Production of a polymer comprising a chemical structure represented by
formula (XII), which is a formula represented by formula (VII) wherein r
is 0, from a compound represented by formula (VI) wherein r is 0, X.sup.1
and X.sup.3 each is Cl, and X.sup.2 and X.sup.4 each is H (R.sup.4
=R.sup.5 =R.sup.6 =H, M.sup.1 =Na.sup.+):
To 4.35 g of the ion complex form obtained in Example 25, 20 ml of a dry
chloroform was added and 3.17 g (23.7 mmol) of N-chlorosuccinimide (NCS)
was further added. At this time, ammonium
1,3-dichloroisothianaphthene-5-sulfonate was produced in the system but
not isolated, and after heating the system under reflux for 2 hours, a
black blue solution was obtained. After cooling, insoluble materials were
removed from the reaction solution, the organic layer was dried under
reduced pressure, and 200 ml of 0.1N NaOH was added to the solution to
obtain a water-soluble polymer solution. The resulting solution was passed
through an acidic ion-exchange column, and an acid-form aqueous polymer
solution having a pH of 1.8 was obtained. The visible near infrared
absorption spectrum of the resulting solution gave the same doped curve as
in FIG. 7.
Example 27
An aqueous solution of a 10 wt % electroconductive polymer produced in the
same manner as in Example 4 was coated on the surface of a glass plate as
a substrate and dried. After further vacuum drying, the polymer layer was
peeled off from the glass plate to obtain a self-standing film having a
thickness of about 30 .mu.m. The self-standing film had an electric
conductivity (in a four-terminal measurement system) at room temperature
of .sigma.=5.times.10.sup.-2 S/cm. The electric conductivity value of the
self-standing film was constantly maintained in air at room temperature
for 3 months.
Example 28
Production of a compound represented by formula (X), which is a compound
represented by formula (VI) wherein r is 0 (R.sup.4 =C.sub.10 H.sub.21
O--, R.sup.5 =R.sup.6 =H, X.sup.1 =X.sup.2 =X.sup.3 =X.sup.4 =H, M.sup.1
=Na.sup.+):
To 8 ml of a sulfuric acid solution containing 2 ml of fuming sulfuric acid
(20% SO.sub.3) cooled to 20.degree. C. or lower, 500 mg of
5-decyloxy-1,3-dihydroisothianaphthene, which is a known compound, was
gradually added with stirring, followed by stirring for 3 hours at room
temperature. The reaction mixture was poured into 100 ml of ice water, and
thereto was added 14 g of sodium chloride to salt out sodium
5-decyloxy-1,3-dihydroisothianaphthene-6-sulfonate, which was then
isolated by a centrifugal separator and vacuum dried to obtain 180 mg of a
gray powder compound.
Example 29
Production of a polymer containing a chemical structure represented by the
following formula (XII), which is a formula represented by formula (VII)
wherein r is 0 (R.sup.4 =C.sub.10 H.sub.21 O--, R.sup.5 =R.sup.6 =H,
M.sup.1 =H.sup.+):
##STR16##
To a mixture system of 600 mg of ferric chloride, 1 ml of water, 100 mg of
sodium 5-decyloxy-1,3-dihydroisothianaphthene-6-sulfonate, was gradually
added with stirring. After continuing stirring 30 min. at room
temperature, a viscous black reaction mixture was obtained.
The reaction mixture was poured into 10 ml of acetone, and the precipitated
polymer was separated by a centrifugal separator. After drying, the
polymer was dissolved in 100 ml of a 0.1N aqueous NaOH solution, insoluble
materials were removed by centrifugation, and impurities were removed by
passing the solution through a 1-.mu.m filter film. An alkaline solution
containing the polymer was acidified with a 1N HCl solution to convert it
into an H-type polymer. The aqueous solution was extracted with chloroform
3 times to provide 55 mg of the polymer after evaporation.
Example 30
On the surface of a glass plate as a support, an aqueous solution of 1% by
weight of the water-soluble conducting polymer produced in the same manner
as in Example 2 was applied by the use of a spin coater at room
temperature and a revolution number of 1,000 rpm to form a thin film of
about 0.05 .mu.m in thickness (determined by the needle touch method
called Dektak).
This thin film exhibited good adhesiveness to the glass plate support, and
showed a surface resistance of about 7.6.times.10.sup.5
.OMEGA./.quadrature.. The transmittance of the film at 500 nm in the
visible region was 96%. Thus, the polymer yielded an conducting film of
extremely high transparency.
Thin films were prepared in the same manner as above except for the
revolution number of the spin coater. The properties of the films obtained
are shown in Table 3 below.
TABLE 3
______________________________________
Revolution
Film Surface
Numbers Thickness Resistance
Transmittance
(rpm) (.mu.m) (.OMEGA./.quadrature.)
(%, at 500 mn)
______________________________________
500 0.10 4.2 .times. 10.sup.5
93
1000 0.05 7.6 .times. 10.sup.5
96
______________________________________
The electroconductive polymer produced according to the process of the
present invention is a water-soluble and/or organic solvent-soluble
electroconductive polymer having excellent processability. Accordingly,
the polymer is useful in various electroconductive materials or optical
materials which require a precise processing, such as an electrode, a
sensor, an electronics display element, a non-linear optical element, a
photoelectric conversion element, or an antistatic agent. Further,
according to the process of the present invention, not only a homopolymer,
but also a copolymer can be produced; where the compositions of the
components constituting the .pi.-conjugated main chain skeleton of the
copolymer can be easily controlled. Furthermore, the polymer can have a
self-doping function and a stable electric conductivity due to the
sulfonic acid group contained in the polymer. Still further, the
heteropolycyclic compound having a sulfonic acid substituent used as a
starting material is very stable, and particularly useful for the
efficient production of a polymer having a high electroconductivity under
mild conditions.
The electroconductive polymer having a chemical structure represented by
the formula (I), (II) or (III) of the present invention is water-soluble
and is a polymer exhibiting high workability and possessing high
electroconductivity. Thus, it is useful as electrodes, electronic display
elements, nonlinear optical elements, optical conversion elements,
antistatic materials, various conducting materials, and optical materials
which are required to allow precision fabrication.
While the invention has been described in detail and with reference to
specific embodiments thereof, it will be apparent to one skilled in the
art that various changes and modifications can be made therein without
departing from the spirit and scope thereof.
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